Presentation description

Nickel-catalyzed cross electrophilic coupling is a promising method of forging sp2-sp3 C-C bonds from readily available and prevalent starting materials, such as aryl and alkyl chlorides. However, it can be challenging to discern whether a pair of substrates will react productively in these systems due to the complex catalytic cycle. This issue is exacerbated by difficulties associated with studying the catalytic Ni(I) intermediates that are implicated in these reactions, such as disproportionation. One approach to navigating this challenge involves the in-situ study of Ni(I) intermediates through peak-ratio analysis. This is an electroanalytical method which utilizes cyclic voltammetry to probe the rates of elementary steps within a catalytic cycle, such as oxidative addition. Peak-ratio analysis allows for the study of otherwise difficult to access Ni(I) complexes and can be utilized to rapidly collect data and derive relative rate values for various combinations of substrates and nickel complexes. These relative rates can then be correlated with computationally obtained properties of the substrates as well as yields of cross coupling reactions using different combinations of substrates. The correlations obtained through this workflow can then be used to build a predictive model for the expected yield of the cross electrophilic coupling reaction between two given substrates based on their properties. This model would be exceptionally useful in synthesis as it solves the problem of unpredictable reaction outcomes and makes the process of constructing molecules using cross electrophilic coupling much more efficient.